Alkylation of polynuclear aromatic hydrocarbons



R. J. MOORE 2,541,882

ALKmTIoN oF PommucLE/m Anoumc mnnocmous Feb. 13, 1951 Filed March 29. 1948 Patented Feb. 13, 1951 ALKYLATION F POLYNUCLEAR AROMATIC HYDROCARBONS Robert J. Moore, Berkeley, Calif.,v assignor to Shell Development Company, San Francisco, Calif., a corporation of Delaware Application March 29, 1948, Serial No. 17,708

'I'his invention relates to an improved process for the more emcient production of alkyl substituted derivatives of polynuclear aromatic hydrocarbons. It relates more particularly to an improved method for alkylating polynuclear hy" drocarbons having condensed aromatic nuclei with olenic hydrocarbons.

Because of the characteristics and properties peculiar to them, the alkyl substituted derivatives of polynuclear aromatic hydrocarbons in relatively pure state are of prime importance. Their value resides not only in their utility as such in many important fields of. application, but in their usefulness as a starting or intermediate material in the production of a wealth of chemical derivatives. High viscosity index values and excellent oxidation stability render certain alkyl derivatives of polynuclear aromatic hydrocarbons of well-defined structure, such as, for example, the alkyl naphthalenes of particular value as components of high quality lubricants. This is especially true of the polynuclear aromatic compounds having one or more long alkyl side chains with a minimum of branching, Dicetylnaphthalene, for example, has a viscosity in the SAE range of 30 and a viscosity index of about 118.

Realization of the advantages inherent in the large scale utilization of the alkyl substituted polynuclear aromatic hydrocarbons in relatively pure state heretofore generally has been impossible 'due to the lack of a practical source of such materials. Available sources comprised, for example, processes primarily directed to the production of products other than the alkyl substituted polynuclear aromatic hydrocarbons in which these materials are produced in relatively minor amounts as a by-product. Separation-of the desired compounds in a relatively high state of purity from such complex mixtures containing them generally entailed the use of additional costly steps militating against practical utilization of a product thus obtained. Processes have been disclosed directed to the alkylation of aromatic hydrocarbons with oleflns. Such processes, however, though enabling the relatively eicient production of certain alkyl substituted mono-nuclear aromatic hydrocarbons are unsuited to the efficient production of a product consisting essentially, or predominantly, of alkyl substituted polynuclear aromatic hydrocarbons of specic structure or composition. The production of any.

alkyl substituted polynuclear aromatic compounds in such processes is generally not only accompanied by low yields, extremely short catalyst life, and operational difliculties themselves 1s ciaims. (ci. 26o-671) often precluding practical operation of the process, but is furthermore unavoidably limited to the production of a product comprising these desired compounds as a minor proportion of a high-` ly complex mixture from which they are separable only by resort to additional costly procedure. Consequently attempts to make use of the highly advantageous properties peculiar to the alkyl substituted polynuclear aromatic hydrocarbons on a practical scale heretofore generally has been limited to the utilization of the available highly complex fractions, or mixtures, comprising uncontrolled and often minor amounts of such compounds of widely varying structures.

It is an object of the present invention to bring within the realm of practicability the more eilicient production of alkyl substituted polynuclear hydrocarbons having aromatic nuclei.

A further object of the invention is the provision of an improved process for the more eflcient production of products consisting essentially, or predominantly, of alkyl substituted polynuclear aromatic compounds of specic composition.

Still another object of the invention is the pro-- vision of an improved process for the more eilicient production of alkyl substituted polynuclear aromatic compounds having one or more long side chains with a minimum of branching directly connected to a nuclear carbon atom.

A more particular object of the invention is the provision of an improved process for the more eiiicient production of alkyl substituted naphthalenes. Other objects and advantages of the invention wlll become apparent from the following detailed description thereof.

In accordance with the invention a polynuclear aromatic hydrocarbon is contacted with an olen in a reaction zone in the presence of a molar excess of a mono-nuclear aromatic hydrocarbon and an aliphatic hydrocarbon-aluminum halide complex which has been saturated with a mononuclear aromatic hydrocarbon prior to introduction into the reaction zone, at alkylating conditions eecting the selective alkylation of the polynuclear hydrocarbon in the absence of any substantial alkylation of the mono-nuclearr aromatic hydrocarbon.. In a preferred method oi' executing the invention at least a part of the eluence from the reaction zone, comprising an alkyl substituted polynuclear hydrocarbon and catalyst complex. isgintroducedinto a catalyst displacing zone. Within the catalyst displacing zone the reactor eluence is contacted with an additional quantity of mono-nuclear `aromatic l 3 `hydrocarbon thereby displacing substantially all polynuclear hydrocarbons from the catalyst, resulting in the formation of a product phase comprising polynuclear hydrocarbons substantially free oi catalyst and a catalyst phase substantially free of poly/,nuclear hydrocarbons. At least a part of the catalyst phase comprising catalyst complex in admixture with mono-nuclear aromatic hydrocarbon is withdrawn from the catalyst displacing zone and passed to the reaction zone. The product phase is passed from the catalyst displacing zone to a product separating zone.'

Polynuclear aromatic hydrocarbons selectively alkylated in accordance with the invention comprise the class of polynuclear aromatic hydrocarbons containing at least two aromatic nuclei and having a hydrogen atom capable of being replaced by an alkyl group directly connected to a carbon atom in an aromatic nucleus. The aromatic nuclei of the suitable polynuclear aromatic hydrocarbons may contain one or more substituent alkyl groups provided there remains at least one replaceable hydrogen atom on` the aromatic ring. Examples of the suitable polynuclear aromatic hydrocarbons selectively alkylated in accordance with the invention are: naphthalene, anthracene, phenanthrene, acenaphthene, dihydroanthracene, stilbene, fluorene, perylene, picene, diphenyl, their homologues etc. Of the suitable polynuclear aromatic hydrocarbons those having two or more condensed aromatic nuclei are preferred. Particularly preferred are the naphthalene hydrocarbons comprising naphthalene and the suitable alkyl sub-V` stituted naphthalenes, such. as methylnaphthalene, dimethylnaphthalene, trimethylnaphthalene, ethylnaphthalene, diethylnaphthalene, methylethylnaphthalene, propylnaphthalene, isopropylnaphthalene, etc. The use of a polynuclear aromatic hydrocarbon charge comprising a mixture of two or more of the suitable polynuclear aromatic hydrocarbons or of hydrocarbon fractions consisting of, or predominating in, such polynuclear aromatic hydrocarbons is comprised within the scope of the invention.

Mono-oleiins suitable as starting materials for the process of the invention comprise the normally gaseous and normally liquid unsaturated hydrocarbons having two or more carbon atoms to the molecule and containing an olenic bond between two adjacent carbon atoms. Suitable mono-olens of open chain and cyclic structure 'or ow controlling means, etc.

. drocarbon mixtures orfractions containing substantial amounts of the mono-olens. Oleiinic vcharge materials particularly preferred because of the relative ease with which they enter into the desired selective alkylation reaction under the conditions of the invention and the desirability of the resulting alkylated products thereby obtained, are the mono-oleflns having from ve to twenty carbon atoms to the molecule. Of these monoolens those of straight chain structure or having a minimum of branching are particularly preferred.

In order to set forth more fully the nature of the invention reference will be had, in the following detailed description thereof, to the attached drawing wherein the single gure illustrates one ,form of apparatus suitable for its execution.

A polynuclear aromatic hydrocarbon, such as, for example, naphthalene, taken from any suitable source, is introduced into the reaction zone of the system. Although the naphthalene may be introduced into the reaction zone as such in the solid or molten state, in the preferred method of executing the invention the polynuclear aromatic hydrocarbon is introduced into the reaction zone 4 dissolved in a suitable solvent. The solvent is introduced by means of valved line I0 into a chamber li containing a supply of naphthalene. Although any solvent may be employed which does not adversely affect execution of the process, it is preferred to let a portion of the mono-nuclear aromatic hydrocarbon stream forming an essential part of the method of the invention as described fully hereinbelow, function simultaneously as the solvent 'for the naphthalene. Thus the mono-nuclear aromatic hydrocarbon introduced into chamber Il by means of line I0 may consist in part or entirety of the mononuclear aromatic hydrocarbon stream recycled from within the system as described hereinafter. The solution of naphthalene in mono-nuclear aromatic hydrocarbon is passed from chamber f II, through valved lines I2 and I3 into the recomprise, for example, ethylene, propylene, Y

butylene-l, butylene2, isobutylene, the amylenes as pentene-l, pentene-2, S-methyl-butene-l, 2- methyl butene l, 2 methyl butene 2, the hexylenes as hexene-l, hexene-2, hexene-, 3- methyl pentene l, 2 methyl pentene 3, 2 methylpenetene l, 2 methyl pentene 1, 2 methylpentene 2, 3 methylpentene 2, 2,3 dimethyl butene 1 and 2,3 dimethyl butene-2, the heptylenes, the octylenes, the nonylenes, the decylenes, undecylenes, cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, and their homologues, oleilnic polymers, etc. The mono-oleiins may be further substituted by the replacement of one or more of the hydrogen atoms by alkyl, or cycloalkyl groups.

AThe particular mono-olens chosen as charge action zone. The reaction zone may comprise a suitable reaction chamber such as, for example, a reactor i4 `of the mixer type provided with stirring means. Although but one such reactor is shown in the drawing, a plurality of such reactors connected in series or in parallel may be employed.

The olefinic hydrocarbon charge to the system, for example, l-pentene is introduced into reactor I4 yirom an outside source by means of line I E. Essential to the attainment of the objects of the invention is the presence within reactor I4 of a substantial excess of a mono-nuclear aromatic hydrocarbon such as, for example, benzene. The mono-nuclear aromatic hydrocarbon is introduced into reactor I4 by means of line I3.

Although in the present illustrative description benzene has been chosen as the preferred mononuclear aromatic hydrocarbon employed in the process of the invention, any member of the homologous series of mono-nuclear aromatic hydrocarbons may be employed in its stead. Examples of such suitable mono-nuclear aromatic suitable stirring means.

hydrocarbons are; the alkyl substituted benzenes such as, toluene, xylene', ethylbenzene, methylethylbenzene, isopropylbenzene, diethylbenzene, and their homologs, etc.

Within reactor Il selective catalytic allwlating conditions are maintained assuring the selective alkylation of the polynuclear aromatic hydrocarbon with the olefin in the absence of any substantial alkylation of the mono-nuclear aromatic hydrocarbon. The selective alkylating conditions within reactor H are obtained by the use as catalyst of a preformed aliphatic hydrocarbon-aluminum halide complex which has been saturated with a mono-nuclear aromatic hydrocarbon, such as, for example, benzene, prior to introduction into the reaction zone, and which contains substantially no free aluminum halide, and the maintenance of the reactants and the mono-nuclear aromatic hydrocarbon rthe reactor above well-defined minimum proportions.

The aliphatic hydrocarbon-aluminum halide complexes suitable for use in the process of the invention, are obtained by the interaction of an aliphatic hydrocarbon, preferably an olenic hydrocarbon or an aliphatic hydrocarbon giving rise to an intermediate olenic reaction product, and an aluminum halide. Of the aluminum halides, aluminum bromide, aluminum chloride and the mixed halides such as AlClzF, AlClF-z, AlBrrF, etc., are preferred. Aluminum chloride is particularly preferred. 'I'he use of a hydrocarbon other than an aliphatic hydrocarbon such as, for example, an aromatic hydrocarbon in the preparation of the complex has been found unsatisfactory.

The catalyst complex may be prepared within the system. To eiect this aluminum halide, for example, aluminum chloride, is introduced into a suitable vessel such as chamber 20 provided with An aliphatic hydrocarbon, for example, an olefin or an olefin-yielding aliphatic hydrocarbon derivative or compound, such as tertiary butyl chloride, is introduced into chamber 20 by means of valved line 22. 'I'he temperature within chamber 20 may be maintained within'the range of, for example, from about room temperature to about' 150 C. A hydrogen halide, such as hydrogen chloride, is preferably introduced into chamber 20 by means of line 23 leading into line 22, to aid in the complex formation. Within chamber 20 interaction of the aluminum chloride and olen or olefin-yielding compound takes place to result in the formation of an aluminum chloride-aliphatic hydrocarbon complex which is iiuid and oily in appearance. Essential to the attainment of efficient operation of the process is the utilization of a complex which is free of any substantial amount of free aluminum chloride. Sufficient oleiln or olefin-yielding aliphatic hydrocarbon or compounds is, therefore, introduced into chamber 20 to assure the production therein of a complex containing no substantial amount of free aluminum chloride. The absence of isomerization activity for paraffin hydrocarbons, such as n-pentane can be used as a convenient test for the absence of free AlCh in this catalyst.

From chamber 20 the complex is passed through line 24 to a suitable separator such as, for example, separating drum 25, wherein any supernatant hydrocarbons are removed from the lower catalyst phase. Essential to the attainment of efficient operation of the process of the invention is the saturation of the complex with a mononuclear aromatic hydrocarbon prior to its introduction into the reaction zone. It is preferred to employ as the mono-nuclear aromatic hydrocarbon for this purpose the same mono-nuclear aromatic material introduced into the reaction zone and employed as solvent for the naphthalene, thereby enhancing the simplicity and flexibility of the process. Accordingly the catalyst phase is passed from separator 25, through line 26, into a catalyst saturating zone. The catalyst saturating zone may comprise any suitable chamber enabling intimate contact of the complex catalyst and the mono-nuclear aromatic hydrocarbon such as, for example, a mixing column 21 provided with suitable baiiles, packing, trays or the like. Within column 21 the catalyst complex is brought into contact with benzene introduced into the column by means of line 28. Benzene is introduced into column 21 in an amount at least sufiicient to assure complete saturation of the complex. Catalyst complex, now fully saturated with benzene and in admixture with any excess benzene present, is passed from column 21 through lines 3| and 32 into reactor I4.

A particularly effective catalyst was prepared by adding ve parts of tertiary butyl chloride to two yparts of anhydrous aluminum chloride and stirring the mixture at room temperature until hydrogen chloride evolution ceased. The resulting homogeneous complex was then saturated with benzene. One hundred eight grams of benzene was required to saturate completely 112 grams of the complex. Without intending to limit the scope of the invention by any theories advanced herein to set forth more fully the nature of the invention, the effect of the mononuclear aromatic hydrocarbon upon the complex is believed to be more than a mere solvent effect and that compound formation between the aliphatic hydrocarbon-aluminum halide cornplex and the mono-nuclear aromatic hydrocarbon takes place. lGenerally the freshly prepared complex will absorb about 4 moles of benzene per mol of AlCla in the complex.

The olefin and polynuclear aromatic hydrocarbons are introduced into reactor I4 in controlled amounts to maintain the molar ratio of polynuclear aromatic hydrocarbon to olefin therein above 1. Charging about 1.25 to about 3 mols, more preferably from about 1.5 to about 2.5 mols, of polynuclear aromatic hydrocarbon per mol of olen to reactor I4 has been found satisfactory. Higher proportions of the polynuclear aromatic hydrocarbon may, however, be employed. The introduction of the mononuclear aromatic hydrocarbon, such as benzene, into reactor I4 is controlled to maintain the mol ratio of the mono-nuclear aromatic hydrocarbon to the total of olefin and polynuclear aromatic hydrocarbons above l. Thus an amount of mononuclear aromatic hydrocarbon in the range of from about 1.25 to about 4 mols, and more preferably from about 1.5 to about 3 mols, per mol of polynuclear aromatic hydrocarbon in reactor I4 has been found suitable. Higher proportions of the mono-nuclear aromatic hydrocarbon may, however, be introduced into the reactor I4. Particularly preferred alkylatingr conditions comprise the maintenanceA of the olefin, polynuclear aromatic hydrocarbon, and mono-nuclear aromatic hydrocarbon in reactor I4 in the molar ratio of about 1 :2 :4, respectively.

Maintenance of an amount of benzene-saturated catalyst complex in reactor i4 in the range of from about 10% to about 200%, and preferably from about 25% to about 100%, by weight of the total hydrocarbon content therein has been found satisfactory. A higher or lower ratio of catalyst to hydrocarbon may be maintained within the reaction zone, however, within the scope of the invention.

The temperature within reactor I4 is maintained in the range of from about 10 C. to about 150 C. and preferably from about 40 C. to about 100 C. Temperature conditions are maintained in reactor I4 by heating means such as, for example, heat exchangers and 36, and optionally by additional temperature controlling means not shown in the drawing. Atmospheric, subatmospheric or superatmospheric pressures may be employed within reactor I4. The use of a superatmospheric pressuresuiiiciently high to facilitate the i'low of reactants through the system is generally preferred. The time of contact will vary in accordance with the specific nature of reactants employed as well as operating conditions such as temperature. tact time of from about one second to about 60 minutes, and preferably from about 5 minutes to about 2O minutes, has been found satisfactory. Higher or lower contact times may, however, be employed within the scope of the invention.

Hydrogen halide is preferably introduced into the reaction zone by means of line 31 leading into line I3. A- hydrogen halide,for example, hydrogen chloride, in an amount ranging from about 0.1% to about 1% of the hydrocarbon charge to reactor I4 is generally employed. Higher or lower amounts of the hydrogen halide may, however, be employed, within the scope of the invention.

A Under the above-defined conditions the polynuclear aromatic hydrocarbon is selectively alkylated by the olen in the absence of any substantial alkylation or other modification of the mono-nuclear aromatic hydrocarbon. Thus, in the specific application of the invention here stressed, the naphthalene is selectively alkylated by the pentene to amylnaphthalene in the absence of any substantial alkylation of the benzene, notwithstanding the fact that benzene will undergo alkylation in the absence of the polynuclear aromatic hydrocarbon. It has been found that the selective alkylation furthermore proceeds in the absence of substantial side chain isomerization and without any substantial interaction of catalyst and reactants and absorption of reactants by the catalyst. It is believed that the selective alkylation and concomitant advantages are directly attributable to the specific mono-nuclear aromatic hydrocarbon-saturated complex containing substantially no free aluminum halide, and the presence in molar excess of the mono-nuclear aromatic hydrocarbon.

Efiluence from reactor I4 comprising amylnaphthalene, catalyst complex, unreacted naphthalene, benzene, and hydrogen halide, is passed through line 40, provided with suitable heat controlling means, such as a heat exchanger 4I, into a separator 42. Within separator 42 a lower catalyst layer is separated from a supernatant hydrocarbon layer. lThe supernatant hydrocarbon layer is passed from separator 42 through line 43 into accumulator 44.

A part or all of the catalyst layer drawn from separator 42 is recycledthrough valved lines 46 and 32 to the reaction zone. The catalyst phase thus drawn from separator 42 will generally comprise some alkylated naphthalene. In a preferred method of carrying out the process of the invention at least a part of the catalyst phase withdrawn from separator 42 through line 46 is pref- In general a con- -A erably passed into a catalyst displacing zone such. as, for example, a column 48 provided with suitable packing, baiiles, trays, or the like. Within column 48 the catalyst phase is contacted countercurrently with benzene introduced through valued line 49. Substantially all remaining alkylated polynuclear aromatic hydrocarbon will be displaced from the catalyst phase. The treatment of the catalyst phase within column 48 is executed at a temperature in the range of, for example, from about 20 C. to about 150 C. It is preferred, however, to effect the treatment of the satalyst phase at a temperature above about 50 C., and preferably in the range of from about 60 C. to about 90 C. Substantially improved separation of product from catalyst, it has been found, is obtained at the higher temperatures. Heat input into column 48 is obtained by heating means, such as a heat exchanger 50 in line 49, and a closed coil 5I in the lower part of column 48. Improved phase separation within separator 42 is obtained by maintaining the separator contents within the range of elevated temperatures prescribed for the treatment within column 48. Catalyst complex substantially free of alkylated polynuclear aromatic products is taken from the base of column 48 and passed, in part or entirety, through valved lines 53 and 54 into line 28 leading into the catalyst saturator 21.

Material comprising the hydrocarbon product is taken from accumulator 44 and passed through line 55v into a stripper 51. Within stripper 51 an overhead fraction comprising the hydrogen chloride promoter is separated from a liquid fraction comprising alkylate, unconverted reactants and benzene. The hydrogen chloride-containing fraction is taken from stripper 51 through valved line 31 and passed into line I3 leading into the reaction zone. Normally gaseous material comprising hydrogen chloride may be flashed from accumulator 44 and passed through line 58 into recycle line 31. A valve outlet 59 is provided to enable the elimination of normally gaseous materials from the system. A part of the hydrogen chloride stream may be diverted from line 31 through line 60 leading into valved lines 26 and 6I. Fresh hydrogen chloride is introduced into the system by means of valved line 63.

The liquid fraction istaken from the lower part of stripper 51 and passed through line 65 into a fractionator 66. Overhead from column 48, comprising benzene and amylnaphthalene, is passed through line 64 into line 65. Within fractionator 66 there is separated an overhead fraction comprising any unconverted pentene present. a higher boiling fraction comprising amylnaphthalenes, and an intermediate fraction comprising benzene and unconverted naphthalene. The higher boiling fraction comprising amylnaphthalenes is separated from fractionator 66 through valved yline 68 as a final product. The overhead from fractionator 66 may be recycled, in part or entirety, to reactor I4 by means not shown in the drawing. The intermediate fraction separated within fractionator 66 and comprising benzene and unconverted naphthalene is recycled, in part or entirety, through lines 61 and 69 into line I3 leading to the reaction zone. f

In a preferred method of carrying out the process of the invention, at least a part of the intermediate fraction taken from fractionator 66 through line 61 is passed through valved line 10 into a fractionator. 1 I. Within fractionator 1I an overhead fraction comprising benzene is separated from liquid bottoms comprising naphthalene and benzene. Liquid bottoms are taken from i'ractionator 1I through valved line 12 and recycled, in part or entirety, through valved lines 69 and I3, to reactor i4.

Overhead comprising benzene is taken from fractionator 1| and recycled through line l0 to drum Il, and into line l1, 28 and 49 as described above. Make-up benzene is introduced into the system from. an outside source through valved line 15. The amount of benzene taken overhead in fractionator ll is generally controlled to provide suiiicient recycle benzene to function as the solvent for the polynuclear aromatic hydrocarbon charge, the saturating medium for the catalyst complex, and the displacing medium for the catalyst phase. Sufficient benzene is, however, left in the bottoms of fractionator Il to assure the ecient recycling of naphthalene to the reaction zone. If desired, an intermediate fraction comprising any by-products boiling between the boiling temperature of the mono-nuclear aromatic solvent and the polynuclear laromatic hydrocarbon may be separated periodically within fractionator 'll and taken therefrom by means of valved line 16.

The process of the invention thus enables the eiiicient production of alkyl substituted polynuclear aromatic hydrocarbons of specific structure in a high state of purity with a minimum of operative steps. The selectivity of the alkylation, the highly eicient separation of product from catalyst complex, and the continuous utilization of the single substantially unaffected mononuclear aromatic hydrocarbon stream for the purposes of attaining the selective reaction condition solution of charge, complex saturation, and catalyst displacement altogether constitute a process which is not only exceedingly economical but unusually flexible and simple in operation.

The following examples are illustrative of the eiiiciency with which polynuclear aromatic hydrocarbons are alkylated in accordance with the invention:

Example I An oleiin-aluminum chloride complex was prepared by reacting 5 parts of tertiary butyl chloride with 2 parts of anhydrous aluminum chloride. 112.5 g. of the complex thus obtained was saturated with benzene at a temperature of 30 to 40 C. in the presence of added anhydrous HC1. To the resulting benzene-saturated catalyst complex thus obtained there was added slowly with stirring over a period of one hour at a temperature of 30 to 40 C., a mixture containing pentene-1, acenaphthene and benzene in a mol ratio of 0.65:1.26;5.5, respectively. The reaction mixture was separated by stratification at room temperature into a catalyst phase, and the catalyst phase was extracted at a temperature of 70 C. with benzene. Eighty-two per cent of the acenaphthene charged was recovered as acenaphthene and alkyl acenaphthene, and 87% of the pentene charged was recovered as amylacenaphthenes. No substantial benzene alkylation was encountered. The distribution of pentenes in the product was as follows:

10 Example II A benzene-saturated oleiin-alumlnum chloride complex was prepared as described in Example I. To this catalyst there was slowly added with vigorous stirring, at atemperature of from 30 to 40 C., a mixture consisting of pentene-1, naphthalene, and benzene, in a mol ratio of 0.8: 1.6:3.25, respectively. Thirty minutes were required to complete the addition of the reactants, and the resulting mixture was stirred for another thirty minutes. The product was separated from the catalyst complex as described in Example I and distilled. Seventy-two per cent of the pentene charged was recovered as amylnaphthalenes, and 88% of the naphthalene charged was accounted ior. No amylbenzene was found in the product. The amylnaphthalenes obtained consisted of:

Mol Per cent Amylnaphthalene 25.5 Diamylnaphthalene 17.9 Triamylnaphthalene 31.1 Tetraamylnaphthalene 19.5

Example III To the catalyst which had been used in the operation of Example II there was added a mixture consisting of cetene, naphthalene and benzene in a mol ratio of 06:12:32, respectively, under substantially the same conditions employed in the operation of Example II. Distillation of the product .showed that 50% of the cetene charged was converted -to cetylnac-hthalene (B. P. about 320 C. at 1 mm. Hg pressure, 11u20 1.5223) and 26% to dicetylnaphthalene.

Example IV A benzene-saturated olen-aluminum chloride complex was prepared as in Example I. To this catalyst there was added a mixture consisting of prohylene trimer (C9 olen) methylnanhthalene and benzene in a mol ratio of 112:4, respectively, at a temperature in the range of 50 to 70 C. The mixture Was maintained in contact with the catalyst complex for an overall contact time of about one hour. The product was separated from the reaction mixture substantially as set forth in Example I. Seventy mol per cent of thel nro'oylene trimer charged was recovered as alkylated products '73% of which consisted of nnnvlmethylnaphthalene and the remainder of which was a material boiling above 420 C.

Example V A catalyst was prepared by saturating with benzene an olefin-aluminum chloride complex obtained bv reacting 2 parts of anhydrous aluminum chloride with 5 parts of propylene trimer (C9 olefin). To the resulting benzene saturated complex there was added, at a temperature of from 50 to 70 C., a mixture of propylene trimer (C9 olefin), methylnaphthaiene and benzene in a mol ratio of 1:2:4, respectively. After an overall contact time of one hour the product was separated from the reaction mixture substantially as described in Example I. It was -found that 50 E.mol percent of the olen trimer charged was recovered as alylated products, *75% by weight of which was nonylmethylnaphthalene and the rest of which was a residual product which had a boiling temperature above 370 C.

For the purpose of comparison the following are given:

To a well-stirred suspension of 37.5 g. of AlCh in a complex prepared by reacting 5 parts of tertiary butyl chloride with 2 parts of A1013 there was slowly added a mixture consisting of benzene and lpentene in a mol ratio of 2:1. The tem-7 perature was maintained at 30-40 C., and 30 minutes were required to eiect the addition of the charge tothe catalyst. This was followed by an additional 30 minutes of stirring. The upper hydrocarbon layer obtained by stratification was washed with water to remove dissolved AlCla. Distillation of the hydrocarbon product showed the following material balance based upon the charge. The catalyst was found to have increased 81.5% in weight.

Per Cent Per Cent of Benzene oi l-pentene Charged Charged 26. 3 Ben am:

Ppnfenn 8, 7 6. 9 Amylbenzene 13.8 2. 2 Diamylhe'nzene G. 4 2. 2 Tetraamlybenzene 18.0 62. 4 Loss to Catalyst 53. 1

Example VII Y Per Cent Per Cent of Benzene of l-pentene Charged Charged 78. 9 Benmna Pantano 0, 13. 9 Amylbenzene 55. 8 0. Diamylbenzene 4. 1 1. 4 Triaxnylbenzene 16. 4 0.8 Pentaamylbenzene (average) 16. 4 4. 5 Los: 7. 3

Of the pentene charged 92.7% was, therefore, recovered as benzene alkylate.

For the purpose of clarity, all apparatus not essential to a complete understanding of the invention such as, for example, pumps, condensers, feed tanks, and auxiliary processing and control equipment have been omitted from the drawing. It is to be understood that the apparatus shown may be modified as apparent to one skilled in the art without departing from thespirit and scope of the invention. For example, although onlyr two fractionators are shown in the drawing, more than two will generally be employed in the execution of the invention on a practical scale.

The invention claimed is:

1. The process for the production of amylnaphthalene which comprises reacting naphtha. lene in solution in a molar excess of benzene with pentene at a temperature in the range of from about 40 C. to about 100 C., a contact time of from 1 second to about 60 minutes, and a pressure sufficient to maintain at least a substantial part of the reactants in the liquid phase, in the presence of a preformed olefin-aluminum chloride complex which has been pre-saturated with benzene, said complex containing substantially no free aluminum chloride, thereby selectively alkylating said naphthalene with said pentene to form a product comprising amylnaphthalene in the absence of any substantial benzene alklation.

2. The process for the production of alkyl substituted naphthalenes consisting essentially of cetylnaphthalene and dicetylnaphthalene which comprises reacting naphthalene with cetene at a temperature of from about 10 C. to about 150 C., a contact time of from 1 second to about 60 minutes, and a pressure suiilcient to maintain at least a substantial part of the reactants in the liquid phase, while in the presence of benzene, present in molar excess with respect to said naphthalene, and a preformed olefin-aluminum halide complex which has been pre-saturated with benzene, said complex containing substantially no free aluminum halide, thereby selectively alkylating said naphthalene with said cetene with the formation of a product comprising alkyl substituted naphthalenes consisting essentially of cetylnaphthalene and dicetylnaphthalene in the absence of any substantial alkylation of said benzene.

3. The process for the production of yalkyl substituted naphthalene consisting essentially of nonylmethylnaphth-alene which comprises reacting methylnaphthalene with an olefin having nine carbon atoms to the molecule at a temperature of from about 10 C. to about 150 C., a contact time of from 1 second to about 60 minutes, and a pressure suiiicient to maintain at least a substantial part of the reactantsin the liquid phase, while in the presence of benzene, present in molar excess with respect to said methylnaphthalene, and a preformed olefin-aluminum halide complex which has been pre-saturated with benzene, said complex containing substantially no free aluminum halide, thereby selectively alkylating said methylnaphthalene with said olefin with the formation of a product comprising alkyl substituted naphthalene consisting essentially of nonylmethylnaphthalene in the absence of any substantial alkylation of said benzene.

4. The process for the production of alkyl substituted naphthalene which comprises reactingr a naphthalene hydrocarbon with an olefin having at least five carbon atoms to the molecule at a temperature of from about 10 C. to about 150 C., a contact time of from 1 second to about 60 minutes, and a pressure suillcient to maintain at least a substantial part of the reactants inthe liquid phase, whilerin the presence of a mononuclear aromatic hydrocarbon, present in molar excess with respect to said naphthalene' hydrocarbon, and a preformed olefin-aluminum halide complex which has been pre-saturated with a mono-nuclear aromatic hydrocarbon, said complex containing substantially no free aluminum halide, thereby selectivelv alkylating said naphthalene hydrocarbon with said olefln with the formation of a product comprising alkyl substituted naphthalene in the absence of any substantial alkylation of said mono-nuclear aromatic hydrocarbon.

5. lThe process for the production of alkyl substitutednaphthalene which comprises reacting a naphthalene hydrocarbon with an olefin at a temperature of from about 10 C. to about 150 C., a contact time of from 1 second to about 60 minutes, and a. pressure suflicient to maintain at least a substantial part of the reactants in the liquid phase, while in the'presence of a. mononuclear aromatic hydrocarbon, present invv molar excess with respect to said naphthalene hydrocarbon, and a preformed aliphatic hydrocarbonaluminum halide complex which has been presaturated with a mono-nuclear aromatic hydrocarbon, said complex containing substantiallyno i'ree aluminum halide, thereby selectively alkylating said naphthalene hrdrocarbon with said oleiin with the formation of a product comprising alkyl substituted naphthalene in the absence of any substantial alkylation of said mono-nuclear aromatic hydrocarbon.

64 The process for the production of an alkyl substituted polynuclear aromatic hydrocarbon having two or more condensed aromatic nuclei which comprises reacting a. polynuclear aromatic hydrocarbon having at least two condensed aromatic nuclei with an olefin having at least five carbon atoms to the molecule at a temperature of from about C. to about 150 C., a contact time of from 1 second to about 6U minutes, and a pressure sufficient to maintain at least a substantial part of the reactants in the liquid phase. while in the presence of benzene, present in molar excess with respect to said polynuclear'aromatic hydrocarbon, and a preformed olefin-aluminum chloride complex which has been pre-saturated with benzene, said comrlex containing substantially no free aluminum chloride, thereby alkylating said polynuclear aromatic -hydrocarbon with said olefin with the formation of a product comprising alkyl substituted polynuclear aromatic hydrocarbon in the absence of any substantial alkylation of said benzene.

7. The process for the production of an alkyl substituted polynuclear aromatic hydrocarbon having two or more condensed aromatic nuclei which comprises reacting a polynuclear aromatic hydrocarbon having at least two condensed aromatic nuclei with an olen having at least ve carbon atoms to the molecule at a temperature of from about 10 C. to about 150 C., a contact time of from 1 second to about 60 minutes, and a pressure sufficient to maintain at least a substantial part of the reactants in the liquid phase, while in the presence of a mono-nuclear aromatic hydrocarbon, present in molar excess with respect to said polynuclear aromatic hydrocarbon, and a preformed oleiin-aluminum halide complex which has been pre-saturated with a mono-nuclear aromatic hydrocarbon, said complex containing substantially no free aluminum halide, thereby alkylating said polynuclear aromatic hydrocarbon with said olen with the formation of a product comprising alkyl substituted polynuclear aromatic hydrocarbon in the absence of any substantial alkylation of said mono-nuclear aromatic hydrocarbon.

8. The process for the production of an alkyl substituted polynuclear aromatic hydrocarbon having two or more condensed aromatic nucl=i which comprises reacting a polynuclear aromatic hydrocarbon having at least two condensed aromatic nuclei with an olen at a temperature of from about 10 C. to about 150 C. while in thef presence of a mono-nuclear aromatic hydrocarmation oi.' a product comprising alkyl substituted polynuclear aromatic hydrocarbon in the absence of any substantial alkylation of said mononuclear aromatic hydrocarbon. y

9. The process for the production of an alkyl substituted polynuclear aromatic hydrocarbon which comprises reacting a polynuclear aromatic hydrocarbon with an oleiin having at least ve carbon atoms to the molecule at a temperature of from about 10 C. to about 150 C., a contact time of from 1 second to about 60 minutes, and a pressure suiiicient to maintain at least a substantial part of the reactants in the liquid phase, while in the presence of benzene, present in molar excess with respect to said polynuclear aromatic hydrocarbon, and a preformed olen-aluminum halide complex which has been pre-saturated with benzene, said complex containing substantially no free aluminum halide, thereby alkylating said polynuclear aromatic hydrocarbon with said olefin with the formation of a product comprising alkyl substituted polynuclear aromatic hydrocarbon in the absence of any substantial alkylation of said benzene.

10. The process for the production of an alkyl substituted polynuclear aromatic hydrocarbon which comprises reacting a polynuclear aromatic hydrocarbon with an olefin having at least ve carbon atoms to the molecule at a temperature of from about 10 C. to about 150 C., a contact time of from 1 second to about 60 minutes, and a pressure suilicient to maintain at least a substantial part of the reactants in the liquid phase, While in the presence of benzene, present in molar excess with respect to said polynuclear hydrocarbon, and a preformed aliphatic hydrocarbonaluminum halide complex which has been presaturated with benzene, said complex containing substantially no free aluminum halide, thereby selectively alkylating said polynuclear aromatic hydrocarbon with said olefin with the formation of a produlct comprising an alkyl substituted polynuclear aromatic hydrocarbon in the absence of any substantial alkylation of said benzene.

l1. The process for the production of an alkyl substituted polynuclear aromatic hydrocarbon which comprises reacting a polynuclear aromatic hydrocarbon with an olen having at least five carbon atoms to the molecule at a temperature of from about 10 C. to about 150 C., a contact ,time of from l second to about 60 minutes, and a pressure sufficient to maintain at least a substantial part of the reactants in the liquid phase,

while in the presence of a mono-nuclear aromatic hydrocarbon, present in molar excess with respect to saidpolynuclear aromatic hydrocarbon, and a preformed olefin-aluminum halide complex which has been pre-saturated with a mono-nuclear aromatic hydrocarbon, said complex containing substantially no free aluminum halide, thereby alkylating said polynuclear aromatic hydrocarbon with said olei'ln with the formation of a product comprising alkyl substituted polynuclear aromatic hydrocarbon in the absence of any substantial alkylation of said mono-nuclear aromatic hydrocarbon.

12. The process for the production of an alkyl substituted polynuclear aromatic hydrocarbon which comprises reacting a polynuclear aromatic hydrocarbon with an oleiin at a temperature of from about 10 C. to about 150 C. while in the presence of a mono-nuclear aromatic hydrocarbon, present in molar excess with respect to said polynuclear aromatic hydrocarbon, and a preformed aliphatic hydrocarbon-aluminum halide complex which has been presaturated with a mono-nuclear aromatic hydrocarbon, said coinplex containing substantially no free aluminum halide, thereby alkylating said polynuclear aromatic hydrocarbon with said olefin with the formation of a product comprising alkyl substituted polynuclear aromatic hydrocarbon in the absence of any substantial alkylation of said mononuclear aromatic hydrocarbon.

13. The process for the production of alkyl substituted naphthalene which comprises reacting naphthalene with an olefin at a temperature of from Iabout C. to about 150 C., a contact time of from 1 second to,v about 60 minutes, and a pressure suflicient to maintain at least a substantial part of the reactants in the liquid phase, while in the presence of benzene, present in molar -excess with respect to said naphthalene, and a preformed olefin-aluminum halide complex which has been pre-saturated with benzene, said complex containing substantially no free aluminum halide, thereby selectively alkylating said naphthalene with the formation of alkyl substituted naphthalene in the absence of any substantial alkylation of said benzene, thereafter separating the reaction mixture by stratification into a hydrocarbon layer and a catalyst layercomprising naphthalenes, contacting said catalyst layer with benzene under conditions forming a hydrocarbon phase and a catalyst phase substantially free of naphthalenes, and recycling said catalyst phase to said alkylation reaction.

14. The process for the production of alkyl substituted naphthalene which comprises reacting naphthalene with an olefin at a temperature of from about 10 C. to about 150 C., a contact time of from 1 second to about 60 minutes, and a pressure suicient to maintain at least a substantial part of the reactants in the liquid phase, while in the presence of benzene, present in molar excess with respect to said naphthalene and a preformed aliphatic hydrocarbon-aluminum halide complex which has been pre-saturated with benzene, said complex containing substantially no free aluminum halide, thereby selectively alkylating said naphthalene with the formation of alkyl substituted naphthalene in the absence of any substantial alkylation of said benzene, thereafter separating the reaction mixture by ystratication into a hydrocarbon layer and a catalyst layer comprising naphthalenes, contacting said catalyst layer with benzene under conditions forming a hydrocarbon phase and a catalyst phase substantially free of naphthalenes, and recycling said catalyst phase to said alkylation reaction.`

15. The process for the production of an alkyl substituted polynuclear aromatic hydrocarbon having two or more condensed aromatic nuclei which comprises reacting a polynuclear aromatic hydrocarbon having at least two condensed aromatic nuclei with an olefin at a temperature of from about 10 C. to about 150 C., a contact time of from 1 second to about 60 minutes, and a pressure sulcient to maintain at least a substantial part of the reactants in the liquid phase,

16 while in the presence of a mono-nuclear, aromatic hydrocarbon, present in molar excess with respect to said polynuclear aromatic hydrocarbon, and a preformed olefin-aluminum halide complex which 'has been pre-saturated-with a mono-nuclear aromatic hydrocarbon, said complex containing substantially no free aluminum halide, thereby selectively alkylating said polynuclear aromatic hydrocarbon with the formation of an alkyl substituted polynuclear aromatic hydrocarbon in the absence of any substantial alkylation of said mono-nuclear aromatic hydrocarbon, thereafter separating the reaction mixture by stratification into a hydrocarbon layer and a catalyst layer comprising polynuclear aromatic hydrocarbons, contacting said catalyst layer with a mono-nuclear aromatic hydrocarbon under conditions forming a hydrocarbon phase and a catalyst phase substantially free ofpolynuclear aromatic hydrocarbons, and recycling said catalyst phase to said alkylation reaction.

16. 'I'he process for the production of an alkyl substituted polynuclear aromatic hydrocarbon which comprises reacting polynuclear aromatic hydrocarbon with an olefin at a temperature of from about 10 C. to about 150 C., a contact time of from 1 second to about 60 minutes, and a pressure suicient to maintain at least a substantial part of the reactants in the liquid phase, while in the presence of a mono-nuclear aromatic hydrocarbon, present in molar excess with respect to said polynuclear aromatic hydrocarbon, and a preformed aliphatic hydrocarbon-aluminum halide complex which has beenpre-saturated with a mono-nuclear aromatic hydrocarbon, said complex containing substantially no free aluminum halide, thereby selectively alkylating said polynuclear aromatic hydrocarbon with the formation of an alkyl substituted polynuclear aromatic hydrocarbon in the absence of any substantial alkylation of said mono-nuclear aromatic hydrocarbon, thereafter separating the reaction mixture by stratification into a hydrocarbon layer and a catalyst layer comprising polynuclear aromatic hydrocarbons, contacting said catalyst layer with a mono-nuclear aromatic hydrocarbon under conditions forming a hydrocarbon phase and a catalyst phase substantially free of polynuclear aromatic hydrocarbons, and recycling said catalyst phase to said alkylation reaction.

ROBERT J. MOORE.

REFERENCES CITED l The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,306 261 Crawford et al Dec. 22, 1942 2,338,711 dOuville et al. Jan. 11, 1944 2,409 389 Ringham Oct. 15, 1946 2,411,530 Driesbach et al. Nov. 26, 1946 2,419,632 Day Apr. 29, 1947 2,437,356 Hill Mar. 9, 1948 2,438,211 Gorin et al Mar. 23, 1948 2,439,729 Guinot et al Apr. 13, 1948 

1. THE PROCESS FOR THE PRODUCTION OF AMYLNAPHTHALENE WHICH COMPRISES REACTING NAPHTHALENE IN SOLUTION IN A MOLAR EXCESS OF BENZENE WITH PENTENT AT A TEMPERATURE IN THE RANGE OF FROM ABOUT 40* C. TO ABOUT 100* C., AND CONTACT TIME OF FROM 1 SECOND TO ABOUT 60 MINUTES, AND A PRESSURE SUFFICIENT TO MAINTAIN AT LEAST A SUBSTANTIAL PART OF THE REACTANTS IN THE LIQUID PHASE, IN THE PRESENCE OF A PREFORMED OLEFIN-ALUMINUM CHLORIDE COMPLEX WHICH HAS BEEN PRE-SATURATED WITH BENZENE, SAID COMPLEX CONTAINING SUBSTANTIALLY ALKYLATING SAID NAPHTHALENE WITH SAID PENTENE TO FROM A PRODUCT COMPRISING AMYLNAPHTHALENE IN THE ABSENCE OF ANY SUBSTANTIAL BENZENE ALKALTION. 